Crossover Equation and the Vapor Pressure of Supercooled Water

Kalova, Jana; Mareš, Radim

doi:10.1007/s10765-009-0681-4

Cited by 9 publications

(5 citation statements)

References 13 publications

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“…[22], and the isobaric heat capacity was derived from the vapor pressure by means of the Clausius-Clapeyron equation as shown in Ref. [42]. We have verified that the result of the fit in the present temperature range was largely insensitive to the particular empirical extrapolations as discussed in Ref.…”

supporting

confidence: 64%

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling

Goy

Potenza

Dedera³

et al. 2018

Phys. Rev. Lett.

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The fast evaporative cooling of micrometer-sized water droplets in a vacuum offers the appealing possibility to investigate supercooled water-below the melting point but still a liquid-at temperatures far beyond the state of the art. However, it is challenging to obtain a reliable value of the droplet temperature under such extreme experimental conditions. Here, the observation of morphology-dependent resonances in the Raman scattering from a train of perfectly uniform water droplets allows us to measure the variation in droplet size resulting from evaporative mass losses with an absolute precision of better than 0.2%. This finding proves crucial to an unambiguous determination of the droplet temperature. In particular, we find that a fraction of water droplets with an initial diameter of 6379±12 nm remain liquid down to 230.6±0.6 K. Our results question temperature estimates reported recently for larger supercooled water droplets and provide valuable information on the hydrogen-bond network in liquid water in the hard-to-access deeply supercooled regime.

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supporting

confidence: 64%

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling

Goy

Potenza

Dedera³

et al. 2018

Phys. Rev. Lett.

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“…The hypothesized LLCP is located in the deeply supercooled region, the no-man’s land below the temperature of homogeneous nucleation. ,− ,,, Various potential model studies − ,,,,− have demonstrated the existence of an LLCP, and Table provides the reported location of the LLCP in the various long-range all-atom models.…”

Section: Liquid–liquid Transitionmentioning

confidence: 99%

Water: A Tale of Two Liquids

et al. 2016

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Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored.

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“…3 In particular, several authors have made attempts to develop a thermodynamic model for the thermodynamic properties of supercooled water based on the LLCP scenario. [3][4][5][6][7][8] The existence of a liquid-liquid critical point in supercooled water is still being debated, especially in view of some recent simulations. 9,10 The purpose of this article is to demonstrate that a theoretical model based on the presumed existence of a second critical point in water is capable of representing, accurately and consistently, all available experimental thermodynamic property data for supercooled ordinary and heavy water.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of supercooled water

Holten

Bertrand²,

Анисимов³

et al. 2012

The Journal of Chemical Physics

217

225

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We review the available experimental information on the thermodynamic properties of supercooled water and demonstrate the possibility of modeling these thermodynamic properties on a theoretical basis. We show that by assuming the existence of a liquid-liquid critical point in supercooled water, the theory of critical phenomena can give an accurate account of the experimental thermodynamic-property data up to a pressure of 150 MPa. In addition, we show that a phenomenological extension of the theoretical model can account for all currently available experimental data in the supercooled region, up to 400 MPa. The stability limit of the liquid state and possible coupling between crystallization and liquid-liquid separation are also discussed. It is concluded that critical-point thermodynamics describes the available thermodynamic data for supercooled water within experimental accuracy, thus establishing a benchmark for further developments in this area.

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Crossover Equation and the Vapor Pressure of Supercooled Water

Cited by 9 publications

References 13 publications

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling

Water: A Tale of Two Liquids

Thermodynamics of supercooled water

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